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Carbonate-hosted lead-zinc ore deposits

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Carbonate-hosted lead-zinc ore deposits are important and highly valuable concentrations of lead and zinc sulfide ores hosted within carbonate ( limestone , marl , dolomite ) formations and which share a common genetic origin.

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110-397: These ore bodies range from 0.5 million tonnes of contained ore, to 20 million tonnes or more, and have a grade of between 4% combined lead and zinc to over 14% combined lead and zinc. These ore bodies tend to be compact, fairly uniform plug-like or pipe-like replacements of their host carbonate sequences and as such can be extremely profitable mines . This classification of ore deposits

220-426: A gravity survey is often carried out, which is the only geophysical technique which can directly detect MVT deposits. Gravity surveys aim to detect significant accumulations of lead and zinc due to their greater density relative to their surrounding host rocks. Finally, the 'pointy end' of an exploration programme is to drill each and every one of the gravity targets in sequence, with no favour or prejudice given to

330-552: A metallurgical view. Some MVT deposits can, however, be very iron-rich and some sulfide replacement and alteration zones are associated with no lead-zinc at all, resulting in massive accumulations of pyrite-marcasite, which are essentially worthless. There is sometimes an association with quartz veining and colloform silica, however silicate gangue minerals are often rare. The importance and synergies between hydrocarbon source-transport-trap 'fairways' and MVT and Irish Type lead-zinc deposits has been known for several decades. Often

440-435: A Fe face-centered cubic sublattice into which the S 2 ions are embedded. (Note though that the iron atoms in the faces are not equivalent by translation alone to the iron atoms at the corners.) The pyrite structure is also seen in other MX 2 compounds of transition metals M and chalcogens X = O , S , Se and Te . Certain dipnictides with X standing for P , As and Sb etc. are also known to adopt

550-433: A density of 11.34 g/cm , which is greater than that of common metals such as iron (7.87 g/cm ), copper (8.93 g/cm ), and zinc (7.14 g/cm ). This density is the origin of the idiom to go over like a lead balloon . Some rarer metals are denser: tungsten and gold are both at 19.3 g/cm , and osmium —the densest metal known—has a density of 22.59 g/cm , almost twice that of lead. Lead

660-492: A few radioactive isotopes. One of them is lead-210; although it has a half-life of only 22.2 years, small quantities occur in nature because lead-210 is produced by a long decay series that starts with uranium-238 (that has been present for billions of years on Earth). Lead-211, −212, and −214 are present in the decay chains of uranium-235, thorium-232, and uranium-238, respectively, so traces of all three of these lead isotopes are found naturally. Minute traces of lead-209 arise from

770-454: A form of tinder made of stringybark by the Kaurna people of South Australia , as a traditional method of starting fires. Pyrite has been used since classical times to manufacture copperas ( ferrous sulfate ). Iron pyrite was heaped up and allowed to weather (an example of an early form of heap leaching ). The acidic runoff from the heap was then boiled with iron to produce iron sulfate. In

880-586: A foul odor and corrosion of copper wiring. In the United States, in Canada, and more recently in Ireland, where it was used as underfloor infill, pyrite contamination has caused major structural damage. Concrete exposed to sulfate ions, or sulfuric acid, degrades by sulfate attack : the formation of expansive mineral phases, such as ettringite (small needle crystals exerting a huge crystallization pressure inside

990-558: A neutron and become thallium-204; this undergoes beta decay to give stable lead-204; on capturing another neutron, it becomes lead-205, which has a half-life of around 17 million years. Further captures result in lead-206, lead-207, and lead-208. On capturing another neutron, lead-208 becomes lead-209, which quickly decays into bismuth-209. On capturing another neutron, bismuth-209 becomes bismuth-210, and this beta decays to polonium-210, which alpha decays to lead-206. The cycle hence ends at lead-206, lead-207, lead-208, and bismuth-209. In

1100-466: A polyhedral vertex and contributes two electrons to each covalent bond along an edge from their sp hybrid orbitals, the other two being an external lone pair . They may be made in liquid ammonia via the reduction of lead by sodium . Lead can form multiply-bonded chains , a property it shares with its lighter homologs in the carbon group. Its capacity to do so is much less because the Pb–Pb bond energy

1210-409: A replacement mineral in fossils , but has also been identified in the sclerites of scaly-foot gastropods . Despite being nicknamed "fool's gold", pyrite is sometimes found in association with small quantities of gold. A substantial proportion of the gold is "invisible gold" incorporated into the pyrite (see Carlin-type gold deposit ). It has been suggested that the presence of both gold and arsenic

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1320-437: A significant partial positive charge on lead. The result is a stronger contraction of the lead 6s orbital than is the case for the 6p orbital, making it rather inert in ionic compounds. The inert pair effect is less applicable to compounds in which lead forms covalent bonds with elements of similar electronegativity, such as carbon in organolead compounds. In these, the 6s and 6p orbitals remain similarly sized and sp hybridization

1430-584: A simple liquid-phase exfoliation route. This is the first study to demonstrate the production of non-layered 2D-platelets from 3D bulk FeS 2 . Furthermore, they have used these 2D-platelets with 20% single walled carbon-nanotube as an anode material in lithium-ion batteries, reaching a capacity of 1000 mAh/g close to the theoretical capacity of FeS 2 . In 2021, a natural pyrite stone has been crushed and pre-treated followed by liquid-phase exfoliation into two-dimensional nanosheets, which has shown capacities of 1200 mAh/g as an anode in lithium-ion batteries. From

1540-438: A single decay chain). In total, 43 lead isotopes have been synthesized, with mass numbers 178–220. Lead-205 is the most stable radioisotope, with a half-life of around 1.70 × 10  years. The second-most stable is lead-202, which has a half-life of about 52,500 years, longer than any of the natural trace radioisotopes. Bulk lead exposed to moist air forms a protective layer of varying composition. Lead(II) carbonate

1650-449: A structure, with every alternate layer of oxygen atoms absent. Negative oxidation states can occur as Zintl phases , as either free lead anions, as in Ba 2 Pb, with lead formally being lead(−IV), or in oxygen-sensitive ring-shaped or polyhedral cluster ions such as the trigonal bipyramidal Pb 5 ion, where two lead atoms are lead(−I) and three are lead(0). In such anions, each atom is at

1760-461: A superficial resemblance to gold , hence the well-known nickname of fool's gold . The color has also led to the nicknames brass , brazzle , and brazil , primarily used to refer to pyrite found in coal . The name pyrite is derived from the Greek πυρίτης λίθος ( pyritēs lithos ), 'stone or mineral which strikes fire', in turn from πῦρ ( pŷr ), 'fire'. In ancient Roman times, this name

1870-458: Is cubic and was among the first crystal structures solved by X-ray diffraction . It belongs to the crystallographic space group Pa 3 and is denoted by the Strukturbericht notation C2. Under thermodynamic standard conditions the lattice constant a {\displaystyle a} of stoichiometric iron pyrite FeS 2 amounts to 541.87 pm . The unit cell is composed of

1980-431: Is soft and malleable , and also has a relatively low melting point . When freshly cut, lead is a shiny gray with a hint of blue. It tarnishes to a dull gray color when exposed to air. Lead has the highest atomic number of any stable element and three of its isotopes are endpoints of major nuclear decay chains of heavier elements. Lead is a relatively unreactive post-transition metal . Its weak metallic character

2090-590: Is 6 times higher, copper 10 times, and mild steel 15 times higher); it can be strengthened by adding small amounts of copper or antimony . The melting point of lead—at 327.5 °C (621.5 °F) —is very low compared to most metals. Its boiling point of 1749 °C (3180 °F) is the lowest among the carbon-group elements. The electrical resistivity of lead at 20 °C is 192 nanoohm -meters, almost an order of magnitude higher than those of other industrial metals (copper at 15.43 nΩ·m ; gold 20.51 nΩ·m ; and aluminium at 24.15 nΩ·m ). Lead

2200-516: Is a neurotoxin that accumulates in soft tissues and bones. It damages the nervous system and interferes with the function of biological enzymes , causing neurological disorders ranging from behavioral problems to brain damage, and also affects general health, cardiovascular, and renal systems. Lead's toxicity was first documented by ancient Greek and Roman writers, who noted some of the symptoms of lead poisoning , but became widely recognized in Europe in

2310-401: Is a superconductor at temperatures lower than 7.19  K ; this is the highest critical temperature of all type-I superconductors and the third highest of the elemental superconductors. Natural lead consists of four stable isotopes with mass numbers of 204, 206, 207, and 208, and traces of six short-lived radioisotopes with mass numbers 209–214 inclusive. The high number of isotopes

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2420-399: Is a case of coupled substitution but as of 1997 the chemical state of the gold remained controversial. Pyrite gained a brief popularity in the 16th and 17th centuries as a source of ignition in early firearms , most notably the wheellock , where a sample of pyrite was placed against a circular file to strike the sparks needed to fire the gun. Pyrite is used with flintstone and

2530-404: Is a common accessory mineral in igneous rocks, where it also occasionally occurs as larger masses arising from an immiscible sulfide phase in the original magma. It is found in metamorphic rocks as a product of contact metamorphism . It also forms as a high-temperature hydrothermal mineral , though it occasionally forms at lower temperatures. Pyrite occurs both as a primary mineral, present in

2640-420: Is a common constituent; the sulfate or chloride may also be present in urban or maritime settings. This layer makes bulk lead effectively chemically inert in the air. Finely powdered lead, as with many metals, is pyrophoric , and burns with a bluish-white flame. Fluorine reacts with lead at room temperature, forming lead(II) fluoride . The reaction with chlorine is similar but requires heating, as

2750-775: Is a mixed sulfide derived from galena; anglesite , PbSO 4 , is a product of galena oxidation; and cerussite or white lead ore, PbCO 3 , is a decomposition product of galena. Arsenic , tin , antimony , silver , gold , copper , bismuth are common impurities in lead minerals. World lead resources exceed two billion tons. Significant deposits are located in Australia, China, Ireland, Mexico, Peru, Portugal, Russia, United States. Global reserves—resources that are economically feasible to extract—totaled 88 million tons in 2016, of which Australia had 35 million, China 17 million, Russia 6.4 million. Typical background concentrations of lead do not exceed 0.1 μg/m in

2860-426: Is a strong oxidizing agent, capable of oxidizing hydrochloric acid to chlorine gas. This is because the expected PbCl 4 that would be produced is unstable and spontaneously decomposes to PbCl 2 and Cl 2 . Analogously to lead monoxide , lead dioxide is capable of forming plumbate anions. Lead disulfide and lead diselenide are only stable at high pressures. Lead tetrafluoride , a yellow crystalline powder,

2970-404: Is a very soft metal with a Mohs hardness of 1.5; it can be scratched with a fingernail. It is quite malleable and somewhat ductile. The bulk modulus of lead—a measure of its ease of compressibility—is 45.8  GPa . In comparison, that of aluminium is 75.2 GPa; copper 137.8 GPa; and mild steel 160–169 GPa. Lead's tensile strength , at 12–17 MPa, is low (that of aluminium

3080-460: Is about 1 atm . A newer commercial use for pyrite is as the cathode material in Energizer brand non-rechargeable lithium metal batteries . Pyrite is a semiconductor material with a band gap of 0.95 eV . Pure pyrite is naturally n-type, in both crystal and thin-film forms, potentially due to sulfur vacancies in the pyrite crystal structure acting as n-dopants. During the early years of

3190-458: Is accelerated by the action of Acidithiobacillus bacteria which oxidize pyrite to first produce ferrous ions ( Fe ), sulfate ions ( SO 4 ), and release protons (   H , or H 3 O ). In a second step, the ferrous ions ( Fe ) are oxidized by O 2 into ferric ions ( Fe ) which hydrolyze also releasing   H ions and producing FeO(OH). These oxidation reactions occur more rapidly when pyrite

3300-423: Is accounted for by point symmetry groups C 3 i and C 3 , respectively. The missing center of inversion at S lattice sites has important consequences for the crystallographic and physical properties of iron pyrite. These consequences derive from the crystal electric field active at the sulfur lattice site, which causes a polarization of S ions in the pyrite lattice. The polarisation can be calculated on

3410-632: Is also known as Mississippi Valley Type or MVT ore deposits, after a number of such deposits along the Mississippi River in the United States, where such ores were first recognised; these include the famed Southeast Missouri Lead District of southeastern Missouri , and deposits in northeast Iowa , southwest Wisconsin , and northwest Illinois . Similarly Irish-type carbonate lead-zinc ores, exemplified by Lisheen Mine in County Tipperary , are formed in similar ways. The ultimate source of

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3520-554: Is also the fastest growing in terms of the unroasted iron pyrites imports, with a CAGR of +27.8% from 2007 to 2016. In July 2020 scientists reported that they have observed a voltage-induced transformation of normally diamagnetic pyrite into a ferromagnetic material, which may lead to applications in devices such as solar cells or magnetic data storage. Researchers at Trinity College Dublin , Ireland have demonstrated that FeS 2 can be exfoliated into few-layers just like other two-dimensional layered materials such as graphene by

3630-522: Is brighter yellow with a greenish hue when wet and is softer (3.5–4 on Mohs' scale). Arsenopyrite (FeAsS) is silver white and does not become more yellow when wet. Iron pyrite is unstable when exposed to the oxidizing conditions prevailing at the Earth's surface: iron pyrite in contact with atmospheric oxygen and water, or damp, ultimately decomposes into iron oxyhydroxides ( ferrihydrite , FeO(OH)) and sulfuric acid ( H 2 SO 4 ). This process

3740-443: Is brittle, gold is malleable. Natural gold tends to be anhedral (irregularly shaped without well defined faces), whereas pyrite comes as either cubes or multifaceted crystals with well developed and sharp faces easy to recognise. Well crystallised pyrite crystals are euhedral ( i.e. , with nice faces). Pyrite can often be distinguished by the striations which, in many cases, can be seen on its surface. Chalcopyrite ( CuFeS 2 )

3850-445: Is common for the carbon group. The divalent state is rare for carbon and silicon , minor for germanium, important (but not prevailing) for tin, and is the more important of the two oxidation states for lead. This is attributable to relativistic effects , specifically the inert pair effect , which manifests itself when there is a large difference in electronegativity between lead and oxide , halide , or nitride anions, leading to

3960-408: Is consistent with lead's atomic number being even. Lead has a magic number of protons (82), for which the nuclear shell model accurately predicts an especially stable nucleus. Lead-208 has 126 neutrons, another magic number, which may explain why lead-208 is extraordinarily stable. With its high atomic number, lead is the heaviest element whose natural isotopes are regarded as stable; lead-208

4070-531: Is easily extracted from its ores , prehistoric people in the Near East were aware of it . Galena is a principal ore of lead which often bears silver. Interest in silver helped initiate widespread extraction and use of lead in ancient Rome . Lead production declined after the fall of Rome and did not reach comparable levels until the Industrial Revolution . Lead played a crucial role in the development of

4180-414: Is exploited in the synthesis of other lead compounds. Few inorganic lead(IV) compounds are known. They are only formed in highly oxidizing solutions and do not normally exist under standard conditions. Lead(II) oxide gives a mixed oxide on further oxidation, Pb 3 O 4 . It is described as lead(II,IV) oxide , or structurally 2PbO·PbO 2 , and is the best-known mixed valence lead compound. Lead dioxide

4290-449: Is finely dispersed (framboidal crystals initially formed by sulfate reducing bacteria (SRB) in argillaceous sediments or dust from mining operations). Pyrite oxidation by atmospheric O 2 in the presence of moisture ( H 2 O ) initially produces ferrous ions ( Fe ) and sulfuric acid which dissociates into sulfate ions and protons , leading to acid mine drainage (AMD). An example of acid rock drainage caused by pyrite

4400-467: Is illustrated by its amphoteric nature; lead and lead oxides react with acids and bases , and it tends to form covalent bonds . Compounds of lead are usually found in the +2 oxidation state rather than the +4 state common with lighter members of the carbon group . Exceptions are mostly limited to organolead compounds . Like the lighter members of the group, lead tends to bond with itself ; it can form chains and polyhedral structures. Since lead

4510-502: Is more prevalent than most other elements with atomic numbers greater than 40. Primordial lead—which comprises the isotopes lead-204, lead-206, lead-207, and lead-208—was mostly created as a result of repetitive neutron capture processes occurring in stars. The two main modes of capture are the s- and r-processes . In the s-process (s is for "slow"), captures are separated by years or decades, allowing less stable nuclei to undergo beta decay . A stable thallium-203 nucleus can capture

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4620-453: Is not a formally recognised mineral, and is named after the Peruvian scientist Jose J. Bravo (1874–1928). Pyrite is distinguishable from native gold by its hardness, brittleness and crystal form. Pyrite fractures are very uneven , sometimes conchoidal because it does not cleave along a preferential plane. Native gold nuggets , or glitters, do not break but deform in a ductile way. Pyrite

4730-650: Is not stable, as both the lead(III) ion and the larger complexes containing it are radicals . The same applies for lead(I), which can be found in such radical species. Numerous mixed lead(II,IV) oxides are known. When PbO 2 is heated in air, it becomes Pb 12 O 19 at 293 °C, Pb 12 O 17 at 351 °C, Pb 3 O 4 at 374 °C, and finally PbO at 605 °C. A further sesquioxide , Pb 2 O 3 , can be obtained at high pressure, along with several non-stoichiometric phases. Many of them show defective fluorite structures in which some oxygen atoms are replaced by vacancies: PbO can be considered as having such

4840-741: Is over three and a half times lower than that of the C–C bond . With itself, lead can build metal–metal bonds of an order up to three. With carbon, lead forms organolead compounds similar to, but generally less stable than, typical organic compounds (due to the Pb–C bond being rather weak). This makes the organometallic chemistry of lead far less wide-ranging than that of tin. Lead predominantly forms organolead(IV) compounds, even when starting with inorganic lead(II) reactants; very few organolead(II) compounds are known. The most well-characterized exceptions are Pb[CH(SiMe 3 ) 2 ] 2 and plumbocene . The lead analog of

4950-465: Is reduced and results in these elements being expelled into the fluid, which becomes saturated in zinc, lead, iron and sulfur. Sulfide minerals such as galena , sphalerite , marcasite and pyrite thus form. Commonly MVT deposits form by the combination of hydrocarbon pyrolysis liberating zinc-lead ions and sulfur to form an acidic solution which dissolves the host carbonate formation and replaces it with massive sulfide accumulations. This may also take

5060-457: Is relatively complex in theory and straightforward in practise. During the area selection phase, attention must be paid to the nature of the carbonate sequences, especially if there is a 'dolomite front' alteration identified within oil exploration wells, which is commonly associated with lead-zinc mineralisation. Thereafter, attention must be paid to picking floral facies of any reef carbonates formed from coral reef accumulations. The facies of

5170-430: Is sprayed onto the exposed coal surfaces to reduce the hazard of dust explosions . This has the secondary benefit of neutralizing the acid released by pyrite oxidation and therefore slowing the oxidation cycle described above, thus reducing the likelihood of spontaneous combustion. In the long term, however, oxidation continues, and the hydrated sulfates formed may exert crystallization pressure that can expand cracks in

5280-415: Is stable, but less so than the difluoride . Lead tetrachloride (a yellow oil) decomposes at room temperature, lead tetrabromide is less stable still, and the existence of lead tetraiodide is questionable. Some lead compounds exist in formal oxidation states other than +4 or +2. Lead(III) may be obtained, as an intermediate between lead(II) and lead(IV), in larger organolead complexes; this oxidation state

5390-413: Is still energetically favorable. Lead, like carbon, is predominantly tetravalent in such compounds. There is a relatively large difference in the electronegativity of lead(II) at 1.87 and lead(IV) at 2.33. This difference marks the reversal in the trend of increasing stability of the +4 oxidation state going down the carbon group; tin, by comparison, has values of 1.80 in the +2 oxidation state and 1.96 in

5500-480: Is suspected to be derived from clastic red bed sequences (potential metal source) that contain evaporites (potential sulfur source). Two potential transportation mechanisms for the metal-bearing ore fluid have been proposed. The first involves compaction of sediments in basins with rapid sedimentation. Mineralizing fluids within the basin become trapped within discrete, over-pressured aquifers and escape episodically and rapidly. The second fluid transportation mechanism

5610-419: Is the 2015 Gold King Mine waste water spill . Pyrite oxidation is sufficiently exothermic that underground coal mines in high-sulfur coal seams have occasionally had serious problems with spontaneous combustion . The solution is the use of buffer blasting and the use of various sealing or cladding agents to hermetically seal the mined-out areas to exclude oxygen. In modern coal mines, limestone dust

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5720-448: Is the heaviest stable nucleus. (This distinction formerly fell to bismuth , with an atomic number of 83, until its only primordial isotope , bismuth-209, was found in 2003 to decay very slowly.) The four stable isotopes of lead could theoretically undergo alpha decay to isotopes of mercury with a release of energy, but this has not been observed for any of them; their predicted half-lives range from 10 to 10 years (at least 10 times

5830-529: Is the origin of the English word " plumbing ". Its ease of working, its low melting point enabling the easy fabrication of completely waterproof welded joints, and its resistance to corrosion ensured its widespread use in other applications, including pharmaceuticals, roofing, currency, warfare. Writers of the time, such as Cato the Elder , Columella , and Pliny the Elder , recommended lead (and lead-coated) vessels for

5940-525: Is the so-called inert pair effect : the 6s electrons of lead become reluctant to participate in bonding, stabilising the +2 oxidation state and making the distance between nearest atoms in crystalline lead unusually long. Lead's lighter carbon group congeners form stable or metastable allotropes with the tetrahedrally coordinated and covalently bonded diamond cubic structure. The energy levels of their outer s- and p-orbitals are close enough to allow mixing into four hybrid sp orbitals. In lead,

6050-430: Is to us. Heinz Eschnauer and Markus Stoeppler "Wine—An enological specimen bank", 1992 Pyrite The mineral pyrite ( / ˈ p aɪ r aɪ t / PY -ryte ), or iron pyrite , also known as fool's gold , is an iron sulfide with the chemical formula Fe S 2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral . Pyrite's metallic luster and pale brass-yellow hue give it

6160-440: Is topographically-driven gravitational fluid flow. This occurs during uplift that is commonly associated with an orogenic event. One edge of a basin is uplifted during the formation of a foreland fold and thrust belt, and basinal fluids migrate laterally away from the deformation front as the basin is uplifted. Migration of the fluids through deep portions of the basin may result in the acquisition of metals and sulfur contained within

6270-566: Is used to make marcasite jewelry . Marcasite jewelry, using small faceted pieces of pyrite, often set in silver , has been made since ancient times and was popular in the Victorian era . At the time when the term became common in jewelry making, "marcasite" referred to all iron sulfides including pyrite, and not to the orthorhombic FeS 2 mineral marcasite which is lighter in color, brittle and chemically unstable, and thus not suitable for jewelry making. Marcasite jewelry does not actually contain

6380-446: Is usefully exploited: lead tetraacetate is an important laboratory reagent for oxidation in organic synthesis. Tetraethyllead, once added to automotive gasoline, was produced in larger quantities than any other organometallic compound, and is still widely used in fuel for small aircraft . Other organolead compounds are less chemically stable. For many organic compounds, a lead analog does not exist. Lead's per-particle abundance in

6490-608: The Phoenicians worked deposits in the Iberian peninsula ; by 1600 BC, lead mining existed in Cyprus , Greece , and Sardinia . Rome's territorial expansion in Europe and across the Mediterranean, and its development of mining, led to it becoming the greatest producer of lead during the classical era , with an estimated annual output peaking at 80,000 tonnes. Like their predecessors,

6600-659: The Solar System is 0.121  ppb (parts per billion). This figure is two and a half times higher than that of platinum , eight times more than mercury , and seventeen times more than gold . The amount of lead in the universe is slowly increasing as most heavier atoms (all of which are unstable) gradually decay to lead. The abundance of lead in the Solar System since its formation 4.5 billion years ago has increased by about 0.75%. The solar system abundances table shows that lead, despite its relatively high atomic number,

6710-401: The nucleus , and more shielded by smaller orbitals. The sum of the first four ionization energies of lead exceeds that of tin, contrary to what periodic trends would predict. This is explained by relativistic effects , which become significant in heavier atoms, which contract s and p orbitals such that lead's 6s electrons have larger binding energies than its 5s electrons. A consequence

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6820-593: The printing press , as movable type could be relatively easily cast from lead alloys. In 2014, the annual global production of lead was about ten million tonnes, over half of which was from recycling. Lead's high density, low melting point, ductility and relative inertness to oxidation make it useful. These properties, combined with its relative abundance and low cost, resulted in its extensive use in construction , plumbing , batteries , bullets , shots , weights , solders , pewters , fusible alloys , lead paints , leaded gasoline , and radiation shielding . Lead

6930-476: The supergene zone. MVT and Irish type deposits are commonly associated with a 'dolomite front' alteration, which manifests as a yellow-cream wash of dolomite (calcium-magnesium carbonate) within calcite-aragonite assemblages of unaltered carbonate formations. Most ore bodies are quite sulfidic, and most are very low-iron, with pyrite - marcasite contents typically below 30% of the mass of sulfides. This makes MVT lead-zinc deposits particularly easy to treat from

7040-468: The +4 state. Lead(II) compounds are characteristic of the inorganic chemistry of lead. Even strong oxidizing agents like fluorine and chlorine react with lead to give only PbF 2 and PbCl 2 . Lead(II) ions are usually colorless in solution, and partially hydrolyze to form Pb(OH) and finally [Pb 4 (OH) 4 ] (in which the hydroxyl ions act as bridging ligands ), but are not reducing agents as tin(II) ions are. Techniques for identifying

7150-522: The 15th century, new methods of such leaching began to replace the burning of sulfur as a source of sulfuric acid . By the 19th century, it had become the dominant method. Pyrite remains in commercial use for the production of sulfur dioxide , for use in such applications as the paper industry , and in the manufacture of sulfuric acid. Thermal decomposition of pyrite into FeS ( iron(II) sulfide ) and elemental sulfur starts at 540 °C (1,004 °F); at around 700 °C (1,292 °F), p S 2

7260-432: The 20th century, pyrite was used as a mineral detector in radio receivers, and is still used by crystal radio hobbyists. Until the vacuum tube matured, the crystal detector was the most sensitive and dependable detector available—with considerable variation between mineral types and even individual samples within a particular type of mineral. Pyrite detectors occupied a midway point between galena detectors and

7370-606: The Egyptians had used lead for sinkers in fishing nets , glazes , glasses , enamels , ornaments . Various civilizations of the Fertile Crescent used lead as a writing material , as coins , and as a construction material . Lead was used by the ancient Chinese as a stimulant , as currency , as contraceptive , and in chopsticks . The Indus Valley civilization and the Mesoamericans used it for making amulets ; and

7480-471: The Romans obtained lead mostly as a by-product of silver smelting. Lead mining occurred in central Europe , Britain , Balkans , Greece , Anatolia , Hispania , the latter accounting for 40% of world production. Lead tablets were commonly used as a material for letters. Lead coffins, cast in flat sand forms and with interchangeable motifs to suit the faith of the deceased, were used in ancient Judea . Lead

7590-452: The arrangement of the metal and diatomic anions differ from that of pyrite. Despite its name, chalcopyrite ( CuFeS 2 ) does not contain dianion pairs, but single S sulfide anions. Pyrite usually forms cuboid crystals, sometimes forming in close association to form raspberry-shaped masses called framboids . However, under certain circumstances, it can form anastomosing filaments or T-shaped crystals. Pyrite can also form shapes almost

7700-600: The atmosphere; 100 mg/kg in soil; 4 mg/kg in vegetation, 5 μg/L in fresh water and seawater. The modern English word lead is of Germanic origin; it comes from the Middle English leed and Old English lēad (with the macron above the "e" signifying that the vowel sound of that letter is long). The Old English word is derived from the hypothetical reconstructed Proto-Germanic * lauda- ('lead'). According to linguistic theory, this word bore descendants in multiple Germanic languages of exactly

7810-512: The basin. The trap for carbonate-hosted lead-zinc sulfides is a chemical reaction which occurs as a consequence of concentration of sulfur, often hydrocarbons, and zinc and lead which are absorbed by the hydrocarbons. The hydrocarbons can either leak out of the fault zone or fold hinge, leaving a stockwork of weakly mineralized carbonate-sulfide veins, or can degrade via pyrolysis in place to form bitumens . Once hydrocarbons are converted to bitumen, their ability to chelate metal ions and sulfur

7920-426: The basis of higher-order Madelung constants and has to be included in the calculation of the lattice energy by using a generalised Born–Haber cycle . This reflects the fact that the covalent bond in the sulfur pair is inadequately accounted for by a strictly ionic treatment. Arsenopyrite has a related structure with heteroatomic As–S pairs rather than S-S pairs. Marcasite also possesses homoatomic anion pairs, but

8030-426: The carbonate sequence is critical, as this is controlled mostly by faults which are the ultimate target of exploration. A fore-reef/back-reef transition is the 'sweet spot', and thus depending on the age of the carbonate sequence, familiarity with coral palaeontology is considered essential. Finally, once a basin model of the carbonate sequence is formulated, and the primary basin-margin faults are roughly identified,

8140-438: The concrete pores) and gypsum creates inner tensile forces in the concrete matrix which destroy the hardened cement paste, form cracks and fissures in concrete, and can lead to the ultimate ruin of the structure. Normalized tests for construction aggregate certify such materials as free of pyrite or marcasite. Pyrite is the most common of sulfide minerals and is widespread in igneous, metamorphic, and sedimentary rocks. It

8250-437: The course of the Earth's history, have remained in the crust instead of sinking deeper into the Earth's interior. This accounts for lead's relatively high crustal abundance of 14 ppm; it is the 36th most abundant element in the crust. The main lead-bearing mineral is galena (PbS), which is mostly found with zinc ores. Most other lead minerals are related to galena in some way; boulangerite , Pb 5 Sb 4 S 11 ,

8360-419: The current age of the universe). Three of the stable isotopes are found in three of the four major decay chains : lead-206, lead-207, and lead-208 are the final decay products of uranium-238 , uranium-235 , and thorium-232 , respectively. These decay chains are called the uranium chain , the actinium chain , and the thorium chain . Their isotopic concentrations in a natural rock sample depends greatly on

8470-428: The diiodide . Many lead(II) pseudohalides are known, such as the cyanide, cyanate, and thiocyanate . Lead(II) forms an extensive variety of halide coordination complexes , such as [PbCl 4 ] , [PbCl 6 ] , and the [Pb 2 Cl 9 ] n chain anion. Lead(II) sulfate is insoluble in water, like the sulfates of other heavy divalent cations . Lead(II) nitrate and lead(II) acetate are very soluble, and this

8580-515: The eastern and southern Africans used lead in wire drawing . Because silver was extensively used as a decorative material and an exchange medium, lead deposits came to be worked in Asia Minor from 3000 BC; later, lead deposits were developed in the Aegean and Laurion . These three regions collectively dominated production of mined lead until c.  1200 BC . Beginning c. 2000 BC,

8690-566: The element its chemical symbol Pb . The word * ɸloud-io- is thought to be the origin of Proto-Germanic * bliwa- (which also means 'lead'), from which stemmed the German Blei . The name of the chemical element is not related to the verb of the same spelling, which is derived from Proto-Germanic * laidijan- ('to lead'). Metallic lead beads dating back to 7000–6500 BC have been found in Asia Minor and may represent

8800-413: The first example of metal smelting . At that time, lead had few (if any) applications due to its softness and dull appearance. The major reason for the spread of lead production was its association with silver, which may be obtained by burning galena (a common lead mineral). The Ancient Egyptians were the first to use lead minerals in cosmetics, an application that spread to Ancient Greece and beyond;

8910-430: The group. Lead dihalides are well-characterized; this includes the diastatide and mixed halides, such as PbFCl. The relative insolubility of the latter forms a useful basis for the gravimetric determination of fluorine. The difluoride was the first solid ionically conducting compound to be discovered (in 1834, by Michael Faraday ). The other dihalides decompose on exposure to ultraviolet or visible light, especially

9020-446: The inert pair effect increases the separation between its s- and p-orbitals, and the gap cannot be overcome by the energy that would be released by extra bonds following hybridization. Rather than having a diamond cubic structure, lead forms metallic bonds in which only the p-electrons are delocalized and shared between the Pb ions. Lead consequently has a face-centered cubic structure like

9130-447: The late 19th century AD. A lead atom has 82 electrons , arranged in an electron configuration of [ Xe ]4f 5d 6s 6p . The sum of lead's first and second ionization energies —the total energy required to remove the two 6p electrons—is close to that of tin , lead's upper neighbor in the carbon group . This is unusual; ionization energies generally fall going down a group, as an element's outer electrons become more distant from

9240-560: The latter being stable only above around 488 °C. Litharge is the most commonly used inorganic compound of lead. There is no lead(II) hydroxide; increasing the pH of solutions of lead(II) salts leads to hydrolysis and condensation. Lead commonly reacts with heavier chalcogens. Lead sulfide is a semiconductor , a photoconductor , and an extremely sensitive infrared radiation detector . The other two chalcogenides, lead selenide and lead telluride , are likewise photoconducting. They are unusual in that their color becomes lighter going down

9350-441: The latter is not; this allows for lead–lead dating . As uranium decays into lead, their relative amounts change; this is the basis for uranium–lead dating . Lead-207 exhibits nuclear magnetic resonance , a property that has been used to study its compounds in solution and solid state, including in the human body. Apart from the stable isotopes, which make up almost all lead that exists naturally, there are trace quantities of

9460-420: The mineral marcasite. The specimens of pyrite, when it appears as good quality crystals, are used in decoration. They are also very popular in mineral collecting. Among the sites that provide the best specimens are Soria and La Rioja provinces (Spain). In value terms, China ($ 47 million) constitutes the largest market for imported unroasted iron pyrites worldwide, making up 65% of global imports. China

9570-607: The mineralizing fluid(s) in MVT deposits is unknown. The ore fluids of MVT deposits are typically low temperature (100 °C–150 °C) and have the composition of basinal brines (10–30 wt.% NaCl equivalent) with pH's of 4.5–5 (buffered by host carbonates). This hydrothermal fluid may or may not carry the required sulfur to form sulfide minerals. Mobile hydrocarbons may have played a role in delivering reduced sulfur to certain MVT systems, while methane and other organic matter can potentially reduce sulfate carried by an acidic fluid. The ore fluid

9680-450: The more mechanically complicated perikon mineral pairs. Pyrite detectors can be as sensitive as a modern 1N34A germanium diode detector. Pyrite has been proposed as an abundant, non-toxic, inexpensive material in low-cost photovoltaic solar panels. Synthetic iron sulfide was used with copper sulfide to create the photovoltaic material. More recent efforts are working toward thin-film solar cells made entirely of pyrite. Pyrite

9790-492: The morphology of fault-hosted stockworks, massive tabular replacements and so forth. Porous limestones may form disseminated ores, however most MVT deposits are massive sulfides with knife-like margins between carbonate and sulfide mineralogies. Ore minerals in carbonate replacement deposits are typically lead sulfide, galena , and zinc sulfide sphalerite . Weathered equivalents form anglesite , cerussite , smithsonite , hydrozincite and secondary galena and sphalerite within

9900-533: The neutrons are arranged in complete shells in the atomic nucleus, and it becomes harder to energetically accommodate more of them. When the neutron flux subsides, these nuclei beta decay into stable isotopes of osmium , iridium , platinum . Lead is classified as a chalcophile under the Goldschmidt classification , meaning it is generally found combined with sulfur. It rarely occurs in its native , metallic form. Many lead minerals are relatively light and, over

10010-706: The original sediments, and as a secondary mineral, deposited during diagenesis . Pyrite and marcasite commonly occur as replacement pseudomorphs after fossils in black shale and other sedimentary rocks formed under reducing environmental conditions. Pyrite is common as an accessory mineral in shale, where it is formed by precipitation from anoxic seawater, and coal beds often contain significant pyrite. Notable deposits are found as lenticular masses in Virginia, U.S., and in smaller quantities in many other locations. Large deposits are mined at Rio Tinto in Spain and elsewhere in

10120-444: The oxidation state of molybdenum is Mo . The mineral arsenopyrite has the formula Fe As S. Whereas pyrite has [S 2 ] units, arsenopyrite has [AsS] units, formally derived from deprotonation of arsenothiol (H 2 AsSH). Analysis of classical oxidation states would recommend the description of arsenopyrite as Fe [AsS] . Iron-pyrite FeS 2 represents the prototype compound of the crystallographic pyrite structure. The structure

10230-528: The perspective of classical inorganic chemistry , which assigns formal oxidation states to each atom, pyrite and marcasite are probably best described as Fe [S 2 ] . This formalism recognizes that the sulfur atoms in pyrite occur in pairs with clear S–S bonds. These persulfide [ S–S ] units can be viewed as derived from hydrogen disulfide , H 2 S 2 . Thus pyrite would be more descriptively called iron persulfide, not iron disulfide. In contrast, molybdenite , Mo S 2 , features isolated sulfide S centers and

10340-418: The preparation of sweeteners and preservatives added to wine and food. The lead conferred an agreeable taste due to the formation of "sugar of lead" ( lead(II) acetate ), whereas copper vessels imparted a bitter flavor through verdigris formation. This metal was by far the most used material in classical antiquity, and it is appropriate to refer to the (Roman) Lead Age. Lead was to the Romans what plastic

10450-414: The presence of the Pb ion in water generally rely on the precipitation of lead(II) chloride using dilute hydrochloric acid. As the chloride salt is sparingly soluble in water, in very dilute solutions the precipitation of lead(II) sulfide is instead achieved by bubbling hydrogen sulfide through the solution. Lead monoxide exists in two polymorphs , litharge α-PbO (red) and massicot β-PbO (yellow),

10560-422: The presence of these three parent uranium and thorium isotopes. For example, the relative abundance of lead-208 can range from 52% in normal samples to 90% in thorium ores; for this reason, the standard atomic weight of lead is given to only one decimal place. As time passes, the ratio of lead-206 and lead-207 to lead-204 increases, since the former two are supplemented by radioactive decay of heavier elements while

10670-417: The prospectivity of particular carbonate formations for lead-zinc deposits of this nature is first identified by core drilling by oil explorers. This concept of a cogeneration of hydrocarbons and precursor brines by the same process allows many lead-zinc explorers to use hydrocarbon basin models to predict if a carbonate sequence is likely to host MVT or Irish Type mineralization. Exploration for MVT deposits

10780-685: The pyrite structure. The Fe atoms are bonded to six S atoms, giving a distorted octahedron. The material is a semiconductor . The Fe ions is usually considered to be low spin divalent state (as shown by Mössbauer spectroscopy as well as XPS). The material as a whole behaves as a Van Vleck paramagnet , despite its low-spin divalency. The sulfur centers occur in pairs, described as S 2 . Reduction of pyrite with potassium gives potassium dithioferrate , KFeS 2 . This material features ferric ions and isolated sulfide (S ) centers. The S atoms are tetrahedral, being bonded to three Fe centers and one other S atom. The site symmetry at Fe and S positions

10890-432: The r-process (r is for "rapid"), captures happen faster than nuclei can decay. This occurs in environments with a high neutron density, such as a supernova or the merger of two neutron stars . The neutron flux involved may be on the order of 10 neutrons per square centimeter per second. The r-process does not form as much lead as the s-process. It tends to stop once neutron-rich nuclei reach 126 neutrons. At this point,

11000-541: The resulting chloride layer diminishes the reactivity of the elements. Molten lead reacts with the chalcogens to give lead(II) chalcogenides. Lead metal resists sulfuric and phosphoric acid but not hydrochloric or nitric acid ; the outcome depends on insolubility and subsequent passivation of the product salt. Organic acids, such as acetic acid , dissolve lead in the presence of oxygen. Concentrated alkalis dissolve lead and form plumbites . Lead shows two main oxidation states: +4 and +2. The tetravalent state

11110-636: The rock and lead eventually to roof fall . Building stone containing pyrite tends to stain brown as pyrite oxidizes. This problem appears to be significantly worse if any marcasite is present. The presence of pyrite in the aggregate used to make concrete can lead to severe deterioration as pyrite oxidizes. In early 2009, problems with Chinese drywall imported into the United States after Hurricane Katrina were attributed to pyrite oxidation, followed by microbial sulfate reduction which released hydrogen sulfide gas ( H 2 S ). These problems included

11220-511: The same as a regular dodecahedron , known as pyritohedra, and this suggests an explanation for the artificial geometrical models found in Europe as early as the 5th century BC. Cattierite ( Co S 2 ), vaesite ( Ni S 2 ) and hauerite ( Mn S 2 ), as well as sperrylite ( Pt As 2 ) are similar in their structure and belong also to the pyrite group. Bravoite is a nickel-cobalt bearing variety of pyrite, with > 50% substitution of Ni for Fe within pyrite. Bravoite

11330-507: The same meaning. There is no consensus on the origin of the Proto-Germanic * lauda- . One hypothesis suggests it is derived from Proto-Indo-European * lAudh- ('lead'; capitalization of the vowel is equivalent to the macron). Another hypothesis suggests it is borrowed from Proto-Celtic * ɸloud-io- ('lead'). This word is related to the Latin plumbum , which gave

11440-459: The sheared contact of carbonates with siliciclastic sequences. Examples include the Dharwar Basin zinc-lead deposits, India where sulfides are hosted in shears within dolomite sequences. Lead Lead (pronounced "led") is a chemical element ; it has symbol Pb (from Latin plumbum ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead

11550-491: The similarly sized divalent metals calcium and strontium . Pure lead has a bright, shiny gray appearance with a hint of blue. It tarnishes on contact with moist air and takes on a dull appearance, the hue of which depends on the prevailing conditions. Characteristic properties of lead include high density , malleability, ductility, and high resistance to corrosion due to passivation . Lead's close-packed face-centered cubic structure and high atomic weight result in

11660-588: The simplest organic compound , methane , is plumbane . Plumbane may be obtained in a reaction between metallic lead and atomic hydrogen. Two simple derivatives, tetramethyllead and tetraethyllead , are the best-known organolead compounds. These compounds are relatively stable: tetraethyllead only starts to decompose if heated or if exposed to sunlight or ultraviolet light. With sodium metal, lead readily forms an equimolar alloy that reacts with alkyl halides to form organometallic compounds such as tetraethyllead. The oxidizing nature of many organolead compounds

11770-560: The strength or amplitude of any anomaly. It is well known that unsubtle and unsophisticated methods of pattern drilling have found MVT deposits missed by more selective explorers, for instance the Lennard Shelf Deposits in Western Australia were found on the second last hole of an extensive drilling programme. Similar deposit styles may be encountered in sheared and deformed carbonate belts where zinc-lead sulfides are hosted at

11880-403: The very rare cluster decay of radium-223, one of the daughter products of natural uranium-235, and the decay chain of neptunium-237, traces of which are produced by neutron capture in uranium ores. Lead-213 also occurs in the decay chain of neptunium-237. Lead-210 is particularly useful for helping to identify the ages of samples by measuring its ratio to lead-206 (both isotopes are present in

11990-498: Was applied to several types of stone that would create sparks when struck against steel ; Pliny the Elder described one of them as being brassy, almost certainly a reference to what is now called pyrite. By Georgius Agricola 's time, c.  1550 , the term had become a generic term for all of the sulfide minerals . Pyrite is usually found associated with other sulfides or oxides in quartz veins , sedimentary rock , and metamorphic rock , as well as in coal beds and as

12100-522: Was used to make sling bullets from the 5th century BC. In Roman times, lead sling bullets were amply used, and were effective at a distance of between 100 and 150 meters. The Balearic slingers , used as mercenaries in Carthaginian and Roman armies, were famous for their shooting distance and accuracy. Lead was used for making water pipes in the Roman Empire ; the Latin word for the metal, plumbum ,

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